Method of preparing high softening point thermoplastics

ABSTRACT

High softening point thermoplastic materials are prepared by the contacting of steam-cracked tar or fractions thereof with oxygen containing gases in the presence of a catalyst comprising salts of iron, copper, aluminum and zinc. The product materials result from the oxidative polymerization which occurs at temperatures in the range of 200* to 300* C. and are useful binder materials for the manufacture of fiberboard and other products.

United States Patent 1191 Dickakian ]March 20, 1973 54 METHOD OF PREPARING IHGH 1,778,329 10/1930 Mason ..260/82 SOFTENING POINT 1,965,191 7/1934 Hyman ..260/82 2,011,053 8/1935 Hyman ..260/82 THERMOPLASTICS 2,828,293 3/ 1958 Leary ..260/82 [75] Inventor: Ghazi Mourad Dickakian, Sterre- 2,387,237 10/1945 Ault ..260/82 beck, Belgium 2,387,259 10/1945 Hall et a1 ..260/82 a ,7 2, 3,238,116 3/1966 Hamner et a1 ....208/6 Asslgneel lsso Research and Ewneermg 3,350,295 10/1967 I-Iamner et a1 ..208/4 ompany OTHER PUBLICATIONS [22] Filed: May 3, 1971 Scheffler, Chem. ABS. 58 (1963) pp. 8653c 21 Appl. No.1 139,866

Primary ExaminerI-Iarry Wong, Jr. 7 [30] Foreign Application priority Data Attorney-Chasan & Sinnock and Michael Conner May 5, 1970 Great Britain ..21,629/70 57 BS 52 us. Cl. ..260/82, 117/132, 117/140, High Softening P thermoplastic materials are 117/161, 260/302, 260/336 UA prepared by the contacting of steam-cracked tar or 51 Int. Cl. ..cosr 15/42 fractions thereof with mil/gen containing gases in [58] Field of Search ..260/82 Plesence of a catalyst comprising Salts of iron copper aluminum and zinc. The product materials result from 56 1 References Cited the oxidative polymerization which occurs at temperatures in the range of 200 to 300 C. and are useful UNITED STATES PATENTS binder materials for the manufacture of fiberboard 1,627,054 5 1927 Morrell et a1 ..260/82 and other products 1,689,599 10/ 1928 Ramage ..260/82 8 Claims, No Drawings 1,868,879 7/1'932 Broadhead et a1. ..260/82 1,888,044 11/1932 Morrell ..260/82 METHOD OF PREPARING HIGH SOFTENING POINT THERMOPLASTICS The invention relates to the conversion of tar and tar fractions derived from steam-cracked gas oil and naphtha or mixtures thereof into more useful products like high softening point thermoplastics. It is an important object of this invention to convert such steamcracked tar and fractions thereof into products with useful properties, which are solid, brittle, high polarity, high carbon (Conradson), high softening point thermoplastics, by reacting them with oxygen or oxygen containing gases, preferably in the presence of a catalyst.

It is a particular advantage of the present invention that practically the whole viscous steam-cracked tar derived from gas oil and naphtha or mixtures thereof can be converted into solid high softening point thermoplastics with very high yields close to the theoretical value.

Accordingly the invention comprises a highly economic method of converting steam-cracked tar derived from gas oil and naphtha or mixtures thereof into more useful products such as high softening point polymeric thermoplastics with a high carbon (Conradson) content wherein the steam-cracked tar or fractions thereof are reacted with oxygen, or oxygen containing gases, preferably in the presence of a catalyst. It is an advantage of the present process that no solvents are needed so that the reaction, if desired, can be performed in one step. Purification or separation of the final product is not necessary.

The steam-cracked tar which is used as the starting material is obtained as the bottoms product when steam-cracking gas oil, naphtha or mixtures of such petroleum hydrocarbons at a temperature within the range of about 700 l,O C, preferably of about 800 900 C. Typical processes are steam-cracking of gas oil or naphtha at a temperature of 800 to 900 C with a 50 to 70 percent conversion to C olefin and lighter hydrocarbons during relatively short times (seconds) followed by stripping at a temperature of about 200 to 250 C to obtain the tar as a bottom product. Gas oil is to be understood as the liquid petroleum distillate with a viscosity and boiling range between kerosene and lubricating oil, and having a boiling range of about 200 to 400 C. Naphtha is a generic term for refined, partly refined or unrefined petroleum products and liquid products of natural gas not less than percent of which distil below 175 C, and not less than 95 percent of which distil below 240 C when subjected to distillation according to the standard method referred to as ASTM-D-86.

The yield of the tar varies according to the type of feed to the steam-cracker. When naphtha is used as a feed the yield is about 2 5 wt percent, and when gas oil is used as a feed the yield is about 20 25 wt percent.

The invention is of particular importance for steamcracked tar derived from gas oil or gas oil/naphtha mixtures, which tar is obtained in relatively high quantities and owing to its structure (a viscous, highly aromatic liquid) practically unsuitable for further uses. It is mainly used as a fuel and it has thus only fuel value.

The present invention provides thermoplastic products based on steam-cracked tar derived from gas boiling fractions of the tar contain aromatics an'd naphthenics in a ratio of about 12 40: l .0. The figures.

may differ from one tar to another depending on the feed material from which it is derived and the conditions during steam-cracking. They illustrate, however, the general characteristics of this type of steamcracked tar.

The tar can be distilled under reduced pressure to give a liquid fraction (b.p. 200 480 C, 760 mm Hg) and a high softening point pitch with a b.p. of 480 C (the pitch content of a steam-cracked tar derived from gas oil is approximately 30 50 wt percent).

The following table gives the chemical compositions of three tar fractions:

Fraction 250-370 370480 480 b.p.

( C 760 mm) Wt in steam-cracked tar 30 27 13.5 6.5 22.3 Molecular;

Weight (Mn) 240 257 534 620 1172 Aromatic] 1.8 2.5 6.0 8.2 15.9 mole Naphthenic/ 1.9 l .6 1.8 0.2 1.3 mole Aromatic] 0.05:1.0 1.56:1.0 3.3:l.0 41:1.0 l2.2:l.0 naphthenic Three Fractions separated by chromatography.

As stated already also the composition of steamcracked tar varies according to the nature of the feed to the steam-cracker and cracking conditions. Broadly the physical characteristics can be indicated by the following ranges, which represent steam-cracked tars derived According to the most important aspect of the present invention steam-cracked tar or fractions thereof as well as blends of the whole tar and tar fractions derived from gas oil or naphtha or mixtures thereof are polymerized to solid, brittle thermoplastics which have high softening points (up to C) and high carbon Conradson content (30 60 wt percent), and which or-excellently suitable as binding materials.

The reaction is of the type of an oxidative polymerization at elevated temperatures using oxygen or oxygen containing gases or an oxygen releasing compound, preferably. in the presence of a catalyst.

Suitably air, or a combination of air and oxygen is injected under vigorous and continuous agitation at a rate of about 0.3 15, preferably 0.35 3.0 cc/minutes/gm of tar expressed as air into the steamcracked tar products heated to 200 300 C, preferably in the presence of a catalyst.

The polymerization is allowed to proceed until a product with the desired softening point is obtained (generally about one-half to 16 hours) depending on air rate, temperature, agitation and catalyst content. The oxygen content of the final product will be in the range of 0.5 to 2.5 wt percent.

The polymerization can be either catalytic or noncatalytic but catalytic polymerization reduces substantially the reaction times to arrive at a desired softening point so thatit is preferred to use a catalyst. Catalysts comprise salts of iron, copper, aluminum and zinc, such as chlorides and nitrates. Particularly effective are iron salts like ferric chloride and ferric nitrate. Ferric l. Specific gravity 1.10-1.25 2. Break point Fraass C) 1-20 3. Ductility at 25 C (cm) 0.1-1.0 4. Softening point (Ring and Ball) C 40-170 5. Penetration at 25 C/IOO #5 sec. (mn) 1-3 6. Carbon (Conradson) wt 30-60 7. Coking value (Alcan method wt 30-60 8. Ash content (wt 0.05-0.5 9. Oxygen content (wt 0.5-2.5 10. Sulfur content (wt 0.1-4.0

11. Aromatics protons/total saturated 1002125 to 100-150 protons ratio (NMR) 12. Beta-resin content (wt 5-20 Note Beta-resin is the difference between the benzene insoluble and quinoline insoluble.

The reaction can be performed in one step because purification or separation of the polymeric product is not necessary. If desired, however suitable solvents may be added.

Conveniently, atmospheric pressure is used, but higher pressures may be used, if desired.

The thermoplastic products are especially of importance as binders for various materials. Apart from the increased softening point and carbon Conradson content the oxidative polymerization introduces polar groups into the product which can be expressed as beta-resin content (difference between benzene insoluble content and quinoline insoluble content). These polar groups are important parameters in determining the adhesive properties of the themtoplastic product in relation to surfaces of pulp fiber, metals as well as coke and coal surfaces. The beta-resin content in the oxidized product varies from 5 to wt percent. It is an advantage that the softening points of the products according to the invention can be varied within the wide range of 40 170 C to suit various uses.

Thus the products of the invention can be used satisfactorily as binders in mechanical pulp to make fiberboard (insulation material) or to make fiber impregnated pipes for drainage. An interesting application is their use as binders for coal dust to produce smokeless coal briquettes or coke briquettes. In such a process coal, the binder and water, usually in the form of steam are mixed at a temperature of about C, whereafter the mixture is pressed into briquettes (green briquettes) which are then subjected to curing at a temperature of about 300 400 C during about 1 to 4 hours. The baked briquettes are used as a solid fuel material. The binders according to the invention when used for the above purpose provide green briquettes with a high crushing strength (200 250 lbs) and baked briquettes which apart from having a high crushing strength are smokeless when used as a solid fuel for domestic or industrial uses. The green briquettes as well as the cured ones can be further subjected to coking at a temperature of about 800 to 1,000 C (for about 10 to 60 min.) to produce coke briquettes.

The products according to the invention may be used as binders solely or in combination with other binders, like coal tar pitch, asphalt and thermosetting or thermoplastic resins, the product according to the invention forming the major compound.

It is an important advantage of the present invention that the whole viscous steam-cracked tar can be converted in one step into useful high-softening point thermoplastics. It is possible, however, to treat according to the process of the invention fractions of the tar, such as the pitch or the fraction with a b.p. of 370 480 C, as well as blends of the whole tar with either lowor high boiling fractions thereof.

The pitch obtained by a high vacuum distillation of the steam-cracked tar may for example be added to the whole tar to increase its aromatic content.

Especially when polymers are desired with relatively high softening points (above C) and high carbon content (more than 40 percent Conradson), which polymers possess a high thermal stability, it is of advantage to react the high boiling fraction of the steamcracked tar (boiling point 480 C") according to the process of the invention in the presence of a catalyst as above described.

Also the liquid fraction boiling between 370 and 480 C can be polymerized, preferably catalytically, to thermoplastic products with a softening point of 40 to C. According to NMR spectroscopy these liquid middle fractions of the tar contain less aromatics than other fractions (ratio aromatic to naphthenic being about 1.3 to 1). Thus the thermoplastic products from this fraction have somewhat different physical properties, especially noticeable when their softening points are relatively low. They are soluble in non-aromatic solvents and are more flexible (in the lower softening point range) than materials derived from the whole tar, which make them suitable as road binders.

Two types of steam-cracked tar varying in their physical characteristics and chemical compositions were used to illustrate the invention. The oxidativepolymerization of two fractions of steam-cracked tar is also illustrated. For its purpose a higher fraction, a solid (b.p. 480 C") and a second fraction, a liquid (b.p. 370

- 480 C*) were used. Physical data of the four starting materials used are given in Table 1.

Examples 1 to 3 illustrate the catalytic oxidative oxidative polymerization of the liquid tar fraction (b.p. 370 480 C) to high softening point thermoplastics, of which data are given in Table 5. Example 17 illustrates a large-scale trial.

polymerization of steam-cracked tar No. 1 using an- 5 hydrous ferric chloride and 4 to 6 the non-catalytic ox- TABLE I.PHYSICAL DATA OF STEAM-CRACKED TARS idative polymerization of the same tar. Examples 7 and AND FRACTIONS USED IN-THE EXAMPLES I 8 illustrate the catalytic oxidative-polymerization of solid Liquid steam-cracked tar No. 1 using hydrated ferric chloride fraction fraction (Fe(.l1.'6H 2) and Examples 9 and lOillustrate the 10 E? 2: .5%? 4553 same reaction using an aqueous solutlon of ferric Specific gravity Cu" L159 L059 L160 L080 chloride (40 wt percent). The reaction conditions are Sulfur content (wt. I given in Table 2. All reactions were carried with f ggfggfiaigi'f 6511:: ,2 3 "iii; (3}

Asphaltenecontent (nigorous stirring to increase the diffusionof the oxygen heptane insoluble) 29 8 2. 8 50 N in the tar. For this purpose a blade mixer was used N e ayfragemolecmar weight (Mn) 335 286 400-500 150 rowtmg at a Speed of Viscosity (05. at 100 413 430 5o. 0

Examples ll and 12 illustrate the catalytic oxidatlve Car on a on) (w percent) 28. 0 3. 0 50. 0 2. 0 puymerlzation of tar No. 2 which has a low softening Ash Content (wt percent)" 04 Distillation data: point and a carbon (Conradson) content, as lndlcated 20 1131,4703 (wt 1n Table 3. percent) 1s 24 Nil Nil 370430 0. (wt. Examples l3, l4, and 15 illustrate the catalytic 0xpercent) 29 Nil n o o ldative polymerization of the sol1d tar fraction (softenpercent) 52 29 I Derived from gas oil. mg po nt 100 C) and b.p 480 C of WhlCh data are b Derived from gas oil/naphtha blend (my given in Table 4. Example 16 illustrates the catalytic "Liquid at 0 0.

TABLE 2.OXIDATIVE-POLYMERIZATION OF STEAM-CRACKED TAR N0. 1

Polymerization conditions Polymerized tar 8.0. Air rate, Catalyst Yield Soft. point Carbon tar (cc./ (wt. Temp. Time Yield (wt. C.) (Conrad- Example (g.) min-lg.) Type of catalyst percent) C.) (hours) (g.) percent) (R and B) s0 1. 150 13 Anhydrous FeCl; 1.0 230 1.0 143 95 87 3 2 150 13 o 1.0 230 2.5 144 as 40 3. 150 13 do 1.0 230 5.0 143 95 133 54.3 4 150 13 Nil 230 1.0 143 95 57 5 150 13 Nil 230 2. 5 141 94 e9 32 6. 150 13 Nil 230 5. 0 143 95 9s 35 i 150 13 FeChfiHzO 1.0 230 2.5 33 160 55 3. 150 13 FeClafiHzO 0.5 230 2.5 01 12s 43 150 13 40 wt. percent aqueous solution FcClr 1.0 230 2.5 135 )1 169 53.0 10 150 13 do 0.5 230 2.5 135 91 147 53.

TABLE 3.OXlDA'lIVE-POLYMERIZATION OF STEAM-CRACKED TAR NO. 2

Polymerization conditions Polymcrizcd tar S.(.'. An rate Catalyst Yield Soft. tar c. (wt. Temp. Time Yield (wt. point Example (g) min/g. T\p(' ofcatalyst percent) C.) (hours) (g.) percent) C.)

U 150 13 Anhydrous FeCh" 1. 0 230 2. 5 132 87 J1 l2. 150 13 (10.... 1.0 230 5.0 137 92 138 TABLE i oXlDATlvE-PULYNlERlZATlON OF STEAM-CRACKED TAR FRACTION 18.1. 480 C3) Polymerization conditions lolynicrizcd tur fraction Tar Air rate Anhydrous Tcmper- Yield Softening Carbon fraction (cc; FM 11 ature Time Yield (\vt. point (Conradson) Flxamph- (g.) minJg.) wt. prim-lit C.) (hours) (g.) percent) (R and B) (wt. percent) 13. 150 13 l U 230 l. 0 143 J5. 3 123. 8 -14 l4 150 13 1.0 230 2. 5 142 U4. 6 134 H l5 150 13 l. 0 300 2. 5 93. 3 144 50 ABLE 5. OXIDATIVE-POLYMERIZATION 0F LIQUID FRACTION (B.P. 370-480 C.) 0F STEAM-CRACKED TAR Polymerization conditions Iolymerized tar fraction Tar Air rate Catalyst Temper- Yield Soft. point Carbon fraction cc. (wt. ature Time Yield (wt. (R and B) (Conradson) EX-a'=- (g.) mmJg.) Type of catalyst percent) C.) (hours) (g) percent) '1 (wt. percent) 16 13 Anhydrous FeCl-i l 0 230 5.0 132 87 un- 33.6

EXAMPLE 17 45 ton of gas oil steam-cracker tar (sp. gr. at 20 C 1.150 soft. point 24 C, carbon Conradson 30) was introduced into a 50 ton carbon-steel reactor. The catalyst (40 percent aqueous solution of ferric chloride) was pumped into the reactor under the level of the tar, in an amount of 1.0 wt percent.

The catalyst-tar mixture was then heated to 200 C by circulating the tar through a heat exchanger heated with hot gas oil.

Superhead steam was injected at the top of the reactor (350 Kg/hour) during the oxidation for safety reasons.

Air at the rate of 0.35 cc/minute/gram of tar was introduced at the bottom of the reactor to effect the polymerization of the tar.

The temperature in the reactor was controlled at 220 230 C by circulating the tar through a heat exchanger cooled with hot gas oil 150 C).

The softening point of the polymerized tar was determined every hour. Table 6 gives the increase in softening point for a period of 12 hours. The final softening point was 116 118 C (Ring and Ball) the yield of the polymerized tar was 85 percent wt. During the oxidation 13 14 wt percent of light oil was separated as overhead, which oil was condensed and separated from water.

TABLE 6 Time (hrs) Soft. Point C) Ring and Ball 24 'The properties of the final product were as follows Sulfur (wt 1.0-3.5

What is claimed is:

1. Process of preparing thermoplastic materials wherein steam-cracked tar having an initial boiling point between about 200 C. and about 300 C. or higher boiling fractions thereof derived from gas oil or naphtha or mixtures thereof, is oxidatively polymerized at temperatures in the range of 200-300 C. by injection under vigorous agitation of oxygen containing gases at the rate of 0.3 to 15 c.c./minutes/gm. of tar in the presence of a catalyst selected from the group consisting of salts of iron, copper, aluminum and zinc, said catalyst being present in an amount of 0.052.0 wt. percent, during a time period sufficient to raise the softening point to a value within the range of 40-l70" C. (Ring and Ball).

2. Process according to claim 1, wherein the reaction is carried out until 0.5 to 2.5 wt percent of oxygen is introduced in the tar.

3. Process according to claim 1, wherein air is mjected at a rate of 0.35 3 cc/minutes/gm.

4. Process according to claim 1, wherein the steamcracked tar to be polymerized is derived from gas oil/naphtha mixtures, said tar having the following characteristics:

Specific Gravity 0.90-1.20 Viscosity cs a't'100F (38 C) 42-5000 cs at 210 F (94 C) 4.0-36.0 Carbon Conradson wt 2.0-30.0 Number Average Molecular Weight Mn -400 Sulfur Content wt 0.1-4.0 Asphaltene (Heptane-insoluble wt 2-35 Softening Point (Ring and Ball) C 5-40 .5. Process according to claim 1, wherein the high boiling pitch fraction of the tar (b.p. 480 C*) is polymerized.

6. Process according to claim 1, wherein combinations of the whole tar and fractions thereof are polymerized.

7. Process according to claim 1, wherein a middle fraction of the tar with b.p. 370 480 C is polymerized.

8. Process according to claim 1, wherein the catalyst is ferric chloride. 

2. Process according to claim 1, wherein the reaction is carried out until 0.5 to 2.5 wt percent of oxygen is introduced in the tar.
 3. Process according to claim 1, wherein air is injected at a rate of 0.35 - 3 cc/minutes/gm.
 4. Process according to claim 1, wherein the steam-cracked tar to be polymerized is derived from gas oil/naphtha mixtures, said tar having the following characteristics: Specific Gravity 0.90-1.20 Viscosity cs at 100* F (38* C) 42-5000 cs at 210* F (94* C) 4.0-36.0 Carbon Conradson wt % 2.0-30.0 Number Average Molecular Weight Mn 175-400 Sulfur Content wt % 0.1-4.0 Asphaltene (Heptane-insoluble wt % 2-35 Softening Point (Ring and Ball) * C 5-40
 5. Process according to claim 1, wherein the high boiling pitch fraction of the tar (b.p. 480* C ) is polymerized.
 6. Process according to claim 1, wherein combinations of the whole tar and fractions thereof are polymerized.
 7. Process according to claim 1, wherein a middle fraction of the tar with b.p. 370* - 480* C is polymerized.
 8. Process according to claim 1, wherein the catalyst is ferric chloride. 